Nitrilation of hydrocarbons



Patented Sept. 25,1945

m'ramsrron or mnocmons John W. Teter, Chicago, 111., aslignor to Sinclair Reflnin Company, tion or c New York, it! a corpora- No Drawing. Application November 15, 1040. Serial No. 365,785 1 r 10 Claims. (crate-ml This invention relates to the production or organic nitrogen compounds by the treatment of unsaturated hydrocarbons with hydrocyanic acid. More particularly, it relates to a catalytic process whereby hydrocyanic acid is caused to combine with unsaturatedhydrocarbons of the oleilnic type to form nitriles.

Nitriles have extensive and a wide variety oi uses in the industries. Further, by the use oi nitriles as intermediate materials many other important organic chemicals such as alcohols, acids, ketones and dicarboxylic acids used in the the manufacture of nylon may be synthesized.

It is an object of the present invention to decrease the cost oi the production of nitriles by using as the primary raw material in their prof duction hydrocarbons which are relatively abundant and inexpensive.

In the reflning of hydrocarbon oil, for instance in the production of gasoline by cracking, large volumes of mixed gases are produced which contain considerable, proportions of oleflns. I have iound'oleiins oithe type so produced to be particularly advantageous charging material for the production or nitriles in accordance with my in-" vention.

Oleflns such as those present in the tail gases from petroleum cracking process are characterized by the presence or a double bond at the end of the carbon chain. I have found these olefins to be most active and most readily nitrilated under my reaction conditions. However, the unsaturated hydrocarbons which may be transiormed into nitriles in accordance with my invention may be obtained from any available source; for instance, they may be obtained by the dehydration of substantially pure aliphatic organic compoumk, such, ior example, as parafllnic hydrocarbons and aliphatic alcohols. Also, polymer gasoline may be used.

Heretoiore, it has been considered impossible to add hydrocyanic acid directly to an olefinic bond or a hydrocarbon. I have discovered that. it these oleflnie hydrocarbons are treated with anhydrous hydrocyanic acid in the presence of a suitable catalyst, the hydrocyanic acid will combine with the unsaturated hydrocarbon. to iorm nitriles. I am unable to state the precise manner in which this reaction occurs but generally it may be represented by the iormula:

'Under certain operating conditions amines have acid an oleflnic hydrocarbons into intimate contact, with the catalyst over a considerable range a: temperature and pressure conditions. However, the reaction resulting in the production-oi the nltrilesis accompanied by several competing reactions. Specifically, there is a tendency for the hydrocarbons to crack or decompose into lighter, lower boiling hydrocarbons; likewise there is a tendency of the hydrocarbon, to polymerize, to become hydrogenated -or dehydrosenated; and also there is a tendency of the hydrocyanic acid and the nitriles to decompose. I have discovered that the rate and extent or these competing reactions vary with the processing conditions such as temperature and pressure and also with the particular catalyst used. To obtain yields of commercial significance it is essential to employ a selective cataLvst and operating conditions which efiectively promote the nitrilation reaction relative to these competing reactions.

I have found certain metallic catalysts to be useful for this purpose. Cobalt and copper cat- 'alysts appear to he the most efiective. 0f the two, cobalt appears to be superior to copper. The metal which is used as the catalyst preferably is highly dispersed so as to present a relatively large contact surface, and preferably is one which is reducible from its compounds and is rendered active by hydrogenation, so that a compound of the metal may be deposited on asbestos fibers, reduced to the metallic state and the resulting highly dispersed metal then activated by hydrogen.

pared by suspending washed asbestos iibers in an aqueous solution of cobalt acetate to which aqueous sodium hydroxide is added slowly during agitation, following which the mass is filtered,

4 washed with distilled water and then gradually increased in temperature to 650 F. The cobalt -is then reduced to an active catalytic metal by suillcient quantities to maintain, under the reaction temperature, pressures of from approxithe nitrilation of the mately 1000 pounds per square inch to upwards 0! 2000 pounds per square inch. The telnperaturesused are from 400 to 750 F. or higher.

The following specific operations directed to the nitrilation oi dodecene will illustrate the process of my invention, although it must be For example, the cobalt catalyst may be pre- --operation.

a bromine substitution number oi 2.5.

Because 'of the toxic nature of hydrocyanic acid these operations were carried out in' a closed chamber. This chamber was equipped with a glass lining and had a capacity of 1.8 liters.

It was adapted t8 be hermetically sealed and so designed that its contents could be heated to the desired temperature while being agitated and to withstand the pressure or upwards of 2000 pounds per square inch. I

In each of the following operations approximately 100 grams of the catalyit and the indicated predetermined amounts olefin and anhydrous liquid hydrocyanic acid were placed'in the chamber. Nitrogen gas was then forcedinto the chamber in an amount calculated to besufficient to give a predetermined pressure at thespecitlc reaction temperature to be employ d. 'I'he chamber was then sealed and heated with constant agitation. The duration of each of 1 these tests was ten hours during which time the specified temperatures were maintained. and agitation continued.

At the completion of each run the chamber and its contents were cooled to room temperature and gas pressure therein released through 1 a. solu on of caustic soda to absorb any remaining hydrocyanic acid. .A caustic soda solution was then charged into the bomb and thoroughly mixed with the contents thereof for several min- 7 weight based on total amount of oleflnconsumed:

being based u the amount of olefin charge, appearinthe i'o owing tabulation:-

' Table III ,1

Run Na.

1 I a a 4 a Lm boiliiigfraction ....-l---. 13.4 as M 10.1 10.5 Orgnnicnitrogen compound.-. .090 None 1.14 mmmedhztrmcuonnmnw 76.8 64. 38.8 40.1 as Organicnitro compound--- None 0.35 0.04 None None 'Highboiling tion ass 10.4, 52.0 46.5

Organic nitrogen compound... .18 1.02 2.12 2.18 2.85

utes in order to neutralize any remaining acid.

The contents of the chamber were then removed and the organ c reaction-products dried and distilled.

The resultsobtained in five illustrated runs under different operating conditions of temperature, pressure and concentrations and the like, together with the operating conditions'of the respective runspappear in the following tabulation:

Table I Run No.

Temperature .312. 400 550 am vac-1m Pressure --.lbs. per sq. in.. 1,210 2,040 2, 100 2, 100 l, 760 Catalyst 0) l (l 0) Mol. ratioHCN to oleflns.-- l l. 36 1. 0 l. B L 6 Olefin: consumed weight per cent 24 34.8 71.1 81.2 99.41

Organicnitrogencompounds Iormed-.. welght per cent 0. 208 l. 41 8. 46 2. 18 3. 49

! Cobalt.

' Copper.

'Ilie percentages of organic nitrogen compounds formed appearing in the above tabulation are based on the amount of olefin charged ,to the heretofore described, i. e. metal-catalyst deposited on asbestos fibers.

The .olefins not consumed in the operation are recovered and may be used as charge material for a second treatment.

The olefin consumed in the respective operations is accounted for in the following tabulation, the figures representing percentage: by

Table II Run No.

In the production of: v

Organic nitrogen compound .191 .04 8.03 1.88 8.54 Cracked products 13.87 3.70 5.61 10.1 18.0 sentenc 2i ts 12-: .1: o no Loss 6.24 20.72 2.26 3.02, 28.2

Analysis of the liquid products 01' the respective runs was made by first separating the prod-. not by fractional distillation into three fractions designated herein "low boiling fraction, intermediate fractlon and high boiling fraction." The low boiling fraction was that portion or the product boiling below 400 F. The intermediate fraction was taken between 400 and 410 F. and the high boiling fraction was the remainder of the product boiling above 410 F.

The proportions of the three fractions of the respective runs and the percentages of organic nitrogen compound presenbin each fraction, both The percentage of organic nitrogen compounds, if any, resent in the low boiling fraction, is usually r atively small except at the more severe tempemture conditions. .That present in the low boiling fraction of the products of the above runs appeared to consist largely of. amines and The catalyst used was in the form in Table III was calculated as primary octyl amine. as previously stated, it is believed that these aniines are produced by the incidental cracking of previously formed nitriles. However, my invention is not dependent upon the accuracy of such assumption.

The organic nitrogen compounds present in the intermediate and high boiling ,fractlons senerally consist of a mixture of various-nitriles. in the composite product of the foregoing runs the nitriles were found largely in the fraction distilling on. between temperatures of 295 F. to 450 F. at millimeters absolute pressure and the fraction distilling at temperatures above- 490 F. at l millimeter absolute pressure.

' The nitriles boiling .between 295 and 450 F. at.100 millimeters pressure appear to consist primarily of aliphatic nitriies having approximately 13 carbon atoms per molecule. Those boiling within the higher temperature range appear to be largely aromatic or cyclic in character. However, in calculating the percentages of organic nitrogen compound appearing for the intermediate and high boiling fractions of Table 111,

catalyst in the form or a dispersed metal which is reducible from its compounds by means of hydrogen, which has been. rendered active by hydrogenation and selectively promotes the nitrilation reaction.

2. In the production oi. nitriles, the improvement which comprises reacting an oleiine with anhydrous hydrocyanic acid in the presence of a metallic catalyst from the group consisting of copperandcobalt.

3. In the production or nitriles, the improvement which comprises reacting an oleflne with anhydrous hydrocyanic acid in the Presence of copper.

4. In the productian or nitriles, the improvement which comprises reacting an oleiine with anhsldrous hydrocyanic acid in the presence of co 1;.

5. In the production of nitrilesfthe improvemeat which comprises reacting, at an elevated Patent r 2;;s ,7i 1-.

JOHN W. PETER.

meat which comprises reactins. at a temperature or irom about 400' F. to 750' I and under a pressure or from about 1.000 to 2,000,.ibswper square-inch, an oleflne with anhydrous hydrocyanic'acidinthepresenceoi'aca tselected from the group consisting oi copper and cobalt.

I. In the production of nitriles the process comprlslnfi reacting dodecene with anhydrous liquid hydrocyanic acid in the presence of nitrogen gas and or a cobalt catalyst at temperatures or 400-750 I. and pressures of from about 1000 to upwards 01' 2000 pounds per square inch.

8. In the production or nitriles the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the presence or nitrocen gas and of a cobalt catalyst at a temperature oi. approximately 650 1'". and pressure of approximately 2100 pounds per square inch, the molecular ratio 61' hydrocyanic acid to dodeoene being 1.

9. Inxtho production or nitriles the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the presence or nitrogen gas and or a copper catalyst at a temperature or approximately 850 F. and a pressure ofv approximately 2100 pounds per square inch. the molecular ratio of hydrocyenic acid to dodecene being 1.6.

10. In the productiofl o1 nitriies, the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the present of nitrogen gas and a catalyst of the class consisting of cobalt and copper at temperatures of 400- 750 F. and pressures 01' from about 1000 and upwards 01' 2000 pounds per square inch.

JOHN W. 'IE'I'ER.

OERTIFICA'IE OF CORRECTION September 25, 19l ,5.

it is hei-eby certified that error appears. in the printed specification oi the above numbered patent requiring correctionas follows: Page l fi r si A column, column, 10; for

be read 6rd of the case in the Patentornoe.

"present" read --presenco-'-- line 28, for the word "pnoces's' read "processes"; line 2, after "to insert -be-- I and that the said Letters 'iatent.- s h ou1d with this correction therein that theoseme may confer-info P g 311 and second column, line 31',.' c'1a1n si ned and sealed this 131m day of December, A. p. 1915.

(Seal) Leslie Frazer First assistant Commissioner or Patents-.

mediate and high boiling fractions of Table 111,

catalyst in the form or a dispersed metal which is reducible from its compounds by means of hydrogen, which has been. rendered active by hydrogenation and selectively promotes the nitrilation reaction.

2. In the production oi. nitriles, the improvement which comprises reacting an oleiine with anhydrous hydrocyanic acid in the presence of a metallic catalyst from the group consisting of copperandcobalt.

3. In the production or nitriles, the improvement which comprises reacting an oleflne with anhydrous hydrocyanic acid in the Presence of copper.

4. In the productian or nitriles, the improvement which comprises reacting an oleiine with anhsldrous hydrocyanic acid in the presence of co 1;.

5. In the production of nitrilesfthe improvemeat which comprises reacting, at an elevated Patent r 2;;s ,7i 1-.

JOHN W. PETER.

meat which comprises reactins. at a temperature or irom about 400' F. to 750' I and under a pressure or from about 1.000 to 2,000,.ibswper square-inch, an oleflne with anhydrous hydrocyanic'acidinthepresenceoi'aca tselected from the group consisting oi copper and cobalt.

I. In the production of nitriles the process comprlslnfi reacting dodecene with anhydrous liquid hydrocyanic acid in the presence of nitrogen gas and or a cobalt catalyst at temperatures or 400-750 I. and pressures of from about 1000 to upwards 01' 2000 pounds per square inch.

8. In the production or nitriles the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the presence or nitrocen gas and of a cobalt catalyst at a temperature oi. approximately 650 1'". and pressure of approximately 2100 pounds per square inch, the molecular ratio 61' hydrocyanic acid to dodeoene being 1.

9. Inxtho production or nitriles the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the presence or nitrogen gas and or a copper catalyst at a temperature or approximately 850 F. and a pressure ofv approximately 2100 pounds per square inch. the molecular ratio of hydrocyenic acid to dodecene being 1.6.

10. In the productiofl o1 nitriies, the process comprising reacting dodecene with anhydrous liquid hydrocyanic acid in the present of nitrogen gas and a catalyst of the class consisting of cobalt and copper at temperatures of 400- 750 F. and pressures 01' from about 1000 and upwards 01' 2000 pounds per square inch.

JOHN W. 'IE'I'ER.

OERTIFICA'IE OF CORRECTION September 25, 19l ,5.

it is hei-eby certified that error appears. in the printed specification oi the above numbered patent requiring correctionas follows: Page l fi r si A column, column, 10; for

be read 6rd of the case in the Patentornoe.

"present" read --presenco-'-- line 28, for the word "pnoces's' read "processes"; line 2, after "to insert -be-- I and that the said Letters 'iatent.- s h ou1d with this correction therein that theoseme may confer-info P g 311 and second column, line 31',.' c'1a1n si ned and sealed this 131m day of December, A. p. 1915.

(Seal) Leslie Frazer First assistant Commissioner or Patents-. 

